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WO2022024936A1 - Film à base de polyester thermorétractable, étiquette thermorétractable, et corps d'emballage - Google Patents

Film à base de polyester thermorétractable, étiquette thermorétractable, et corps d'emballage Download PDF

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Publication number
WO2022024936A1
WO2022024936A1 PCT/JP2021/027385 JP2021027385W WO2022024936A1 WO 2022024936 A1 WO2022024936 A1 WO 2022024936A1 JP 2021027385 W JP2021027385 W JP 2021027385W WO 2022024936 A1 WO2022024936 A1 WO 2022024936A1
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WO
WIPO (PCT)
Prior art keywords
film
heat
mol
polyester
less
Prior art date
Application number
PCT/JP2021/027385
Other languages
English (en)
Japanese (ja)
Inventor
雅幸 春田
Original Assignee
東洋紡株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to US18/006,521 priority Critical patent/US20230348661A1/en
Priority to JP2022540254A priority patent/JP7364085B2/ja
Priority to EP21849664.4A priority patent/EP4190845A4/fr
Priority to KR1020237006647A priority patent/KR20230042741A/ko
Priority to CN202180059666.2A priority patent/CN116133825A/zh
Publication of WO2022024936A1 publication Critical patent/WO2022024936A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D23/00—Details of bottles or jars not otherwise provided for
    • B65D23/08—Coverings or external coatings
    • B65D23/0842—Sheets or tubes applied around the bottle with or without subsequent folding operations
    • B65D23/0878—Shrunk on the bottle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/02—Wrappers or flexible covers
    • B65D65/22—Details
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
    • B29C61/02—Thermal shrinking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D2203/00—Decoration means, markings, information elements, contents indicators
    • B65D2203/02—Labels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions
    • G09F2003/0272—Labels for containers
    • G09F2003/0273—Labels for bottles, flasks

Definitions

  • the present invention relates to a heat-shrinkable polyester-based film, and more particularly, a heat-shrinkable polyester-based film having high piercing strength when used as a label for PET bottle beverages and having excellent bag-dropping property, and heat-shrinkable. It relates to labels and packages.
  • stretched films made of polyvinyl chloride resin, polystyrene resin, polyester resin, etc. have been used for label packaging, cap seals, integrated packaging, etc. that protect glass bottles and PET bottles and display products.
  • Heat-shrinkable films are becoming widely used.
  • polyvinyl chloride-based films have problems such as low heat resistance and generation of hydrogen chloride gas during incineration, which causes dioxin.
  • polystyrene film is inferior in solvent resistance, it is necessary to use ink with a special composition at the time of printing, and it is necessary to incinerate it at a high temperature, and a large amount of black smoke is generated with an offensive odor at the time of incineration.
  • polyester-based heat-shrinkable films having high heat resistance, easy incineration, and excellent solvent resistance have been widely used as shrinkage labels, and the distribution amount of PET containers has increased. With the increase, the amount used tends to increase.
  • a normal heat-shrinkable polyester film that shrinks significantly in the width direction is widely used.
  • the film is stretched by a tenter stretching method or the like to produce a wide master roll, and then the master roll is slit at an arbitrary width and wound into a roll of an arbitrary length to obtain a film roll product.
  • the film is given a design and is applied to the printing process in the form of a roll for the purpose of displaying the product. After printing, it is slit again to the required width and wound into a roll, then it is made into a tube through a center sealing process by solvent adhesion and wound into a roll (it becomes a roll of a label).
  • the label that was made into a tube and rolled up is cut to the required length while being unwound from the roll, and becomes a label in a ring shape.
  • the annular label is attached to the object to be packaged by a method such as covering with a hand, and is shrunk through a steam tunnel or a hot air tunnel to form a label.
  • the weight of PET bottle containers has been reduced and the thickness of PET bottle containers has also been reduced for the purpose of reducing the amount of garbage.
  • the thickness of the PET bottle container becomes thin, there arises a problem that the PET bottle container is deformed and the label is torn when dropped.
  • a label using a heat-shrinkable film is also required to have a thin thickness in order to reduce the volume.
  • the thickness of the film has also increased from 45 to 60 ⁇ m to 20 to 40 ⁇ m in recent years.
  • the bag-dropping property of the label deteriorates. Therefore, it is important to improve the bag-dropping property of the film.
  • the thickness becomes thin the feeling of waist is lowered, and there is a concern that the label may be bent and the label may be improperly attached in the process of printing the film into a label and then attaching the label to the PET bottle.
  • Patent Document 1 describes a method for improving the bag tear resistance when the film is dropped. According to the report, the piercing strength is an important factor for the bag resistance as a film characteristic. However, what is described in Patent Document 1 is an evaluation of bag breaking resistance when a non-heat-shrinkable film using a composition in which polyester and polybutylene terephthalate are mixed is made into a bag, and the heat-shrinkable film and heat-shrinkage are described. Not mentioned for labels with film.
  • Patent Document 2 describes a method for improving the problem that the label is bent and becomes defective in the process of mounting on a PET bottle. According to it, it is stated that the film strength in the height direction (non-shrinkage direction) when the label is attached is increased by stretching the film in two axes of the non-shrinkage direction and the shrinkage direction. However, in this method, since there is a biaxial stretching step of stretching not only in the film width direction but also in the longitudinal direction, the equipment is inevitably long, which is not preferable.
  • the present invention has a high heat shrinkage rate in the main shrinkage direction, has high film piercing strength, has bag-breaking resistance when a bottle is dropped, and has a high film density, so that it has an excellent heat shrinkage. It is an object of the present invention to provide a sex polyester film.
  • the present invention which solves the above problems, has the following configuration.
  • Ethylene terephthalate unit is contained in 100 mol% of all ester units, 60 mol% or more and 95 mol% or less, and diethylene glycol is contained in 100 mol% of polyhydric alcohol component.
  • a heat-shrinkable polyester-based film containing 5 mol% or more and 40 mol% or less and 0 mol% or more and 5 mol% or less of a constituent unit derived from a monomer component that can be an amorphous component in all polyester resin components.
  • a heat-shrinkable polyester-based film characterized by satisfying the following requirements (1) to (5).
  • the heat shrinkage rate of hot water when the film is immersed in hot water at 90 ° C for 10 seconds is 40% or more and 80% or less in the film width direction.
  • Shrinkage rate is -5% or more and 15% or less in the longitudinal direction of the film
  • Film piercing strength is 0.2 N / ⁇ m or more and 0.6 N / ⁇ m or less
  • Film density is 1.330 g / cm 3 or more 1 .385 g / cm 3 or less (5)
  • Refractive index in the longitudinal direction of the film is 1.575 or less 2.
  • the thickness of the film is 15 ⁇ m or more.
  • the haze at a film thickness of 20 ⁇ m is 2% or more and 10% or less.
  • the heat-shrinkable polyester-based film described in. 4. 1.
  • the puncture strength after shrinking the film by 10% in the width direction is 0.1 N / ⁇ m or more and 0.5 N / ⁇ m or less.
  • ⁇ 3. The heat-shrinkable polyester-based film according to any one of. 5.
  • the above 1. ⁇ 4.
  • the heat-shrinkable polyester film of the present invention not only has a high shrinkage rate, but also has a high piercing strength after shrinking by 10%, so that it is difficult to break the bag even if the label after being attached to the PET bottle falls. Moreover, since the density is high, it is possible to reduce defects when the PET bottle is mounted.
  • the heat-shrinkable polyester film of the present invention will be described in detail.
  • the method for producing the heat-shrinkable polyester film will be described in detail later, but the heat-shrinkable film is usually obtained by transporting and stretching it using a roll or the like.
  • the film transport direction film forming direction
  • the direction orthogonal to the longitudinal direction is referred to as a film width direction. Therefore, the width direction of the heat-shrinkable polyester film shown below is a direction perpendicular to the roll unwinding direction, and the film longitudinal direction is a direction parallel to the roll unwinding direction.
  • the heat-shrinkable polyester film of the present invention contains an ethylene terephthalate unit in 100 mol% of all ester units in an amount of 60 mol% or more and 95 mol% or less, and contains diethylene glycol in 100 mol% of a polyhydric alcohol component in an amount of 5 mol% or more and 40.
  • )-(5) is a heat-shrinkable polyester-based film.
  • the heat shrinkage rate of hot water when the film is immersed in hot water at 90 ° C for 10 seconds is 40% or more and 80% or less in the film width direction.
  • Shrinkage rate is -5% or more and 15% or less in the longitudinal direction of the film
  • Film piercing strength is 0.2 N / ⁇ m or more and 0.6 N / ⁇ m or less
  • Film density is 1.33 g / cm 3 or more 1 .385 g / cm 3 or less (5)
  • Refractive index in the longitudinal direction of the film is 1.575 or less
  • a homopolymer (PET) made of ethylene terephthalate may be copolymerized with another polyvalent carboxylic acid component or another polyhydric alcohol component. It is widely done.
  • the polyhydric alcohol component used as the copolymerizing component for example, neopentyl glycol and 1,4-cyclohexaneditanol are considered and widely used.
  • a film obtained by copolymerizing these components has a higher chemical cost than a diethylene glycol film.
  • neopentyl glycol when a raw material resin obtained by copolymerizing diethylene glycol is obtained, since diethylene glycol is a liquid at room temperature, a melting step essential for a powder raw material such as neopentyl glycol becomes unnecessary. Further, as compared with neopentyl glycol, there is an advantage that the polymerization activity is high and the foaming at the time of polymerization which leads to a decrease in productivity is small. Further, as compared with diethylene glycol, the polyester raw material copolymerized with neopentyl glycol or 1,4-cyclohexaneditanol has a lower density, so that the film formed by the copolymer has a lower density and a poor feeling of waist.
  • the film of the present invention contains ethylene terephthalate as a main component.
  • the main constituent component means that 60 mol% or more of all the polymer constituent components constituting the film is ethylene terephthalate. It is more preferable to contain 65 mol% or more of ethylene terephthalate.
  • PET Polyethylene terephthalate
  • Any production method such as a transesterification method in which an ester (including a methyl ester of another dicarboxylic acid if necessary) and ethylene glycol (including another diol component if necessary) are subjected to a transesterification reaction can be used. ..
  • dicarboxylic acid component other than terephthalic acid constituting the polyester used in the film of the present invention examples include aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid and orthophthalic acid, adipic acid, azelaic acid, sebacic acid and decandicarboxylic acid.
  • aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid and orthophthalic acid, adipic acid, azelaic acid, sebacic acid and decandicarboxylic acid.
  • aliphatic dicarboxylic acids and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid.
  • the content is preferably less than 3 mol%.
  • the heat-shrinkable polyester-based film obtained by using a polyester containing 3 mol% or more of these aliphatic dicarboxylic acids has insufficient film waist when worn at high speed.
  • a polyvalent carboxylic acid having a valence of 3 or more for example, trimellitic acid, pyromellitic acid and anhydrides thereof.
  • the heat-shrinkable polyester-based film obtained by using the polyester containing these multivalent carboxylic acids makes it difficult to achieve the required shrinkage.
  • diethylene glycol is 5 mol% or more and 40 mol% or less in 100 mol% of the polyhydric alcohol component constituting the polyester used in the film of the present invention.
  • diethylene glycol is more preferably 6 mol% or more, and particularly preferably 8 mol% or more.
  • the upper limit of diethylene glycol is high, but if it is too high, there is a concern that activation during polymerization will decrease, foaming, and foreign matter in the melt extrusion process when forming a film, so the upper limit is 40 mol% in the present invention. And said.
  • Examples of the polyhydric alcohol component other than ethylene glycol and diethylene glycol constituting the polyester used in the present invention include 1-3 propanediol, 2,2-diethyl-1,3-propanediol, and 2-n-butyl-2-ethyl.
  • -1,3-Propanediol 2,2-isopropyl-1,3-Propanediol, 2,2-di-n-butyl-1,3-propanediol, 1-4 butanediol, neopentyl glycol, hexanediol
  • aliphatic diols such as, alicyclic diols such as 1,4-cyclohexanedimethanol, and aromatic diols such as bisphenol A.
  • a diol having 8 or more carbon atoms for example, octane diol
  • a polyhydric alcohol having 3 or more valences for example, trimethylolpropane, trimeritol ethane, glycerin, diglycerin, etc.
  • a heat-shrinkable polyester-based film obtained by using a polyester containing these diols or a polyhydric alcohol makes it difficult to achieve the required high shrinkage.
  • various additives such as waxes, antioxidants, antistatic agents, crystal nucleating agents, thickeners, and heat-stabilizing agents are included as required.
  • Agents, coloring pigments, anticoloring agents, ultraviolet absorbers and the like can be added.
  • the inorganic fine particles include silica, alumina, titanium dioxide, calcium carbonate, kaolin, barium sulfate and the like
  • the organic fine particles include, for example, an acrylic resin. Examples thereof include particles, melamine resin particles, silicone resin particles, crosslinked polystyrene particles and the like.
  • the average particle size of the fine particles is in the range of 0.05 to 3.0 ⁇ m (when measured with a Coulter counter), and can be appropriately selected as needed.
  • the particles can be added at any stage of producing the polyester-based resin, but at the stage of esterification or the transesterification reaction. After completion, it is preferable to add it as a slurry dispersed in ethylene glycol or the like at a stage before the start of the transesterification reaction to proceed with the transesterification reaction. Further, a method of blending a slurry of particles dispersed in ethylene glycol or water using a kneaded extruder with a vent and a polyester resin raw material, or a method of blending dried particles and a polyester resin raw material using a kneaded extruder. It is also preferable to use a method of blending with and the like.
  • examples of the monomer that can be an amorphous component include neopentyl glycol, 1,4-cyclohexanedimethanol, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. Acid, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-isopropyl-1,3-propanediol, 2,2-di -n-butyl-1,3-propanediol and hexanediol can also be mentioned.
  • the content of the monomer that can be the amorphous component in the copolymerized polyester is preferably 0 mol% or more and 5 mol% or less, and more preferably not contained (that is, 0 mol%).
  • the heat-shrinkable polyester film of the present invention is the main shrinkage direction of the film calculated by the following formula 1 from the length before and after shrinkage when treated in warm water at 90 ° C. under no load for 10 seconds.
  • the heat shrinkage rate (that is, the heat shrinkage rate of hot water at 90 ° C.) is preferably 40% or more and 80% or less.
  • Heat shrinkage rate ⁇ (length before shrinkage-length after shrinkage) / length before shrinkage ⁇ x 100 (%) ... Equation 1
  • the shrinkage rate of hot water at 90 ° C. is more preferably 43% or more, particularly preferably 46% or more, and most preferably 50% or more. There is no problem if the hot water heat shrinkage rate in the main shrinkage direction at 90 ° C. is higher than 80%, but in the present invention, a film having a hot water heat shrinkage rate of 90 ° C. higher than 80% could not be obtained, so the upper limit is 80. %.
  • the heat-shrinkable polyester film of the present invention preferably has a hot water heat-shrinkage rate of ⁇ 5% or more and 15% or less in the longitudinal direction orthogonal to the main shrinkage direction at 90 ° C. If the shrinkage rate of hot water at 90 ° C. in the longitudinal direction is less than ⁇ 5%, the label is stretched and the label height in the PET bottle becomes long, which is not preferable when used for beverage labels.
  • the shrinkage rate of hot water at 90 ° C. in the longitudinal direction is more preferably -4% or more, and particularly preferably -3% or more. If the shrinkage rate of hot water at 90 ° C.
  • the shrinkage rate of hot water at 90 ° C. in the longitudinal direction is more preferably 13% or less, further preferably 11% or less, particularly preferably 8% or less, and most preferably 5% or less.
  • the heat-shrinkable polyester film of the present invention preferably has a piercing strength of 0.2 N / ⁇ m or more and 0.6 N / ⁇ m or less.
  • the piercing strength shall be measured by the method described in the examples. If it is 0.2 N / ⁇ m or less, a PET bottle label for beverages using a heat-shrinkable film having a thin thickness is not preferable because the label will break if dropped when purchased at a vending machine.
  • the piercing strength is more preferably 0.25 N / ⁇ m or more, and particularly preferably 0.3 N / ⁇ m or more.
  • the heat-shrinkable polyester film of the present invention preferably has a piercing strength of 0.1 N / ⁇ m or more and 0.5 N / ⁇ m or less after the film is shrunk by 10% in the width direction. Since the heat-shrinkable polyester-based film is generally heat-shrinked and used, the film after shrinking at 10% shrinkage is a film assuming a label after shrinking. If the piercing strength is 0.1 N / ⁇ m or less, a PET bottle label for beverages using a thin heat-shrinkable film is not preferable because the label will break if dropped when purchased at a vending machine.
  • the puncture strength of the film after 10% shrinkage is more preferably 0.15 N / ⁇ m or more, and particularly preferably 0.2 N / ⁇ m or more. There is no problem even if the piercing strength of the film after 10% shrinkage is higher than 0.5N / 15mm, but in the present invention, it is not possible to obtain a film having a piercing strength of the film after 10% shrinkage higher than 0.5N / ⁇ m. Therefore, the upper limit was set to 0.5 N / ⁇ m.
  • the heat-shrinkable polyester film of the present invention preferably has a refractive index of 1.575 or less in the longitudinal direction of the film.
  • the refractive index shall be measured by the method described in the examples.
  • the tensile breaking strength of the film increases, but the tensile elongation at breaking of the film decreases. Since the stretchability of the film at tensile break decreases, that is, the film is difficult to stretch (becomes brittle), PET bottle labels for beverages using a thin heat-shrinkable film will break if dropped when purchased at a vending machine. It is not preferable because it is a bag.
  • the film longitudinal direction is the non-shrinkage direction, perforations and notches are often formed so that the label can be easily opened, so that the refractive index in the film longitudinal direction is important.
  • the refractive index in the longitudinal direction of the film is more preferably 1.572 or less, and particularly preferably 1.569 or less.
  • the refractive index in the longitudinal direction of the unstretched film is about 1.55 to 1.56, so that it does not fall below 1.55.
  • the heat-shrinkable polyester film of the present invention preferably has a density of 1.33 g / cm 3 or more. If it is less than 1.330 g / cm 3 , the label using a thin heat-shrinkable film will not have enough waist in the process of attaching it to the PET bottle for beverages, and the label will break or the label will not be fixed in a fixed position. Not preferred.
  • the density of the film is more preferably 1.340 g / cm 3 or more, and particularly preferably 1.350 g / cm 3 or more. A high density of the film is preferable for the waist, but it is preferably 1.385 g / cm 3 or less.
  • the density of the heat-shrinkable polyester film is more preferably 1.384 g / cm 3 or less, and particularly preferably 1.383 g / cm 3 or less.
  • the thickness of the heat-shrinkable polyester film of the present invention is not particularly limited, but is preferably 15 to 50 ⁇ m as the heat-shrinkable film for label applications and bento packaging applications. If the film thickness is less than 15 ⁇ m, the firmness of the film is significantly reduced, and wrinkles are likely to occur in the roll, which is not preferable. On the other hand, although there is no problem as a film roll even if the film thickness is thick, it is preferable to make the film thinner from the viewpoint of cost.
  • the thickness of the film is more preferably 17 to 45 ⁇ m, and particularly preferably 20 ⁇ m to 40 ⁇ m.
  • the heat-shrinkable polyester film of the present invention preferably has a haze value of 2% or more and 10% or less at a thickness of 20 ⁇ m. Since the heat-shrinkable film is a film that gives a design property, if the haze value is higher than 10%, the contents cannot be clearly seen when the label of the PET bottle is used, and the design property is deteriorated, which is not preferable.
  • the haze at a film thickness of 20 ⁇ m is more preferably 8% or less, and particularly preferably 6% or less.
  • the heat-shrinkable polyester film of the present invention can be obtained by melting and extruding the above-mentioned polyester raw material with an extruder to form an unstretched film, and stretching the unstretched film in the width direction.
  • the polyester can be obtained by polycondensing the above-mentioned suitable dicarboxylic acid component and diol component by a known method. Also, usually, chip-shaped polyester is used as a raw material for the film.
  • melt-extruding the raw material resin it is preferable to dry the polyester raw material using a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer. After the polyester raw material is dried in this way, it is melted at a temperature of 230 to 270 ° C. and extruded into a film using an extruder.
  • a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer.
  • the polyester raw material is dried in this way, it is melted at a temperature of 230 to 270 ° C. and extruded into a film using an extruder.
  • any existing method such as the T-die method and the tubular method can be adopted.
  • an unstretched film can be obtained by quenching the sheet-shaped molten resin after extrusion.
  • a method for rapidly cooling the molten resin a method of casting the molten resin from a base onto a rotary drum and quenching and solidifying the molten resin to obtain a substantially unoriented resin sheet can be preferably adopted.
  • the obtained unstretched film can be stretched in the width direction under predetermined conditions to obtain the heat-shrinkable polyester-based film of the present invention.
  • preferable stretching for obtaining the heat-shrinkable polyester-based film of the present invention will be described.
  • a normal heat-shrinkable polyester-based film is produced by stretching an unstretched film in a direction in which it is desired to shrink.
  • a manufacturing method of biaxial stretching in which longitudinal stretching is performed and then transverse stretching is performed, but in the case of biaxial stretching, large-scale equipment is required.
  • uniaxial stretching is performed in the width direction, which is the main contraction direction.
  • the manufacturing means by uniaxial stretching in the width (horizontal) direction has an advantage that it can be manufactured by simple equipment because it does not use stretching equipment in the longitudinal direction.
  • the preheating temperature of the unstretched film is preferably Tg of the film + 30 ° C. or higher and + 80 ° C. or lower. More preferably, it is Tg + 20 ° C. or higher and + 60 ° C. or lower. If the temperature is less than Tg + 30 ° C., the stretching force becomes high due to insufficient preheating temperature, and fracture is likely to occur, which is not preferable.
  • the stretching force in the width direction of the unstretched sheet decreases, and the thickness accuracy (uneven thickness) in the width direction deteriorates, which is not preferable. More preferably, it is Tg +40 or more and + 70 ° C. or less.
  • the film temperature during stretching in the width direction is preferably Tg ° C. or higher and Tg + 30 ° C. or lower. If the film temperature is less than Tg, the stretching force becomes too high and the film is likely to break, which is not preferable. When the film temperature exceeds Tg + 30 ° C., the stretching force is too low, and the heat shrinkage in the width direction measured at 90 ° C. as described above becomes low, which is not preferable. It is more preferably Tg + 3 ° C. or higher and + 25 ° C. or lower, and further preferably Tg + 5 ° C. or higher and + 25 ° C. or lower.
  • the draw ratio in the width direction is preferably 3.5 times or more and 6 times or less. If the draw ratio is less than 3.5 times, the draw force is insufficient and the thickness accuracy in the film width direction (so-called uneven thickness) deteriorates. Further, if the draw ratio exceeds 6 times, the risk of breakage during film formation increases and the equipment becomes long, which is not preferable. More preferably, it is 3.7 times or more and 5.5 times or less. Further, although not particularly limited, heat treatment may be performed to adjust the shrinkage rate after stretching in the width direction.
  • the film temperature during heat fixing is preferably Tg + 50 ° C. or higher than the film stretching temperature in the width direction.
  • the film stretching temperature in the width direction is + 1 ° C. or higher and Tg + 45 ° C. or lower, and more preferably the film stretching temperature in the width direction is + 2 ° C. or higher and Tg + 40 ° C. or lower.
  • the heat shrinkage rate in the longitudinal direction is generated by the residual stress of the stress (so-called necking force) in the direction orthogonal to the stretching direction generated when stretching in the width direction. Therefore, by relaxing in the longitudinal direction when stretching in the width direction, the residual stress in the longitudinal direction can be relaxed and the heat shrinkage rate in the longitudinal direction can be reduced. Relaxing in the longitudinal direction was done while shortening the distance between the clips.
  • the relaxation rate in the longitudinal direction is preferably 0% or more and 4% or less. Even if the relaxation rate in the longitudinal direction is 0%, there is no problem if the heat shrinkage rate in the longitudinal direction is as targeted.
  • the relaxation rate in the longitudinal direction is higher than 4%, the amount of relaxation is higher than the amount of shrinkage of the film, resulting in insufficient relaxation and poor flatness, which is not preferable. More preferably, it is 1% or more and 3% or less. If the relaxation rate is within this range, a film having a particularly high heat shrinkage rate in the width direction and a low heat shrinkage rate in the longitudinal direction can be obtained.
  • the film evaluation method is as follows.
  • Heat shrinkage rate hot water heat shrinkage rate
  • the film is cut into 10 cm ⁇ 10 cm squares, immersed in warm water at a predetermined temperature of ⁇ 0.5 ° C for 10 seconds under no load, heat-shrinked, and then immersed in water at 25 ° C ⁇ 0.5 ° C for 10 seconds. Then, the film was taken out of water and the vertical and horizontal dimensions of the film were measured, and the heat shrinkage was determined according to the following formula (1). The direction in which the heat shrinkage rate was large was defined as the main shrinkage direction.
  • Thermal shrinkage ⁇ (length before shrinkage-length after shrinkage) / length before shrinkage ⁇ x 100 (%) Equation 1
  • the refractive index in the longitudinal direction of the film was measured by an Abbe refractive index meter using diiodomethane as a contact liquid using a sodium D line as a light source.
  • Tg glass transition point
  • Polyesters B to D shown in Table 1 were obtained by the same method as in Synthesis Example 1. During the production of polyester B, SiO2 (Fuji Silysia Chemical Ltd. Silicia 266; average particle size 1.5 ⁇ m) was added as a lubricant at a ratio of 20000 ppm to the polyester. The ultimate viscosities of the polyesters were all 0.70 dl / g. In addition, each polyester was appropriately formed into chips. The composition of each polyester is shown in Table 1.
  • Example 1 The above-mentioned polyester A, polyester B, and polyester C were mixed at a mass ratio of 17: 3: 80 and charged into an extruder. After that, the mixed resin is melted at 270 ° C. using a 4-axis screw, extruded from the T-die while cooling to 260 ° C., wound around a rotating metal roll cooled to a surface temperature of 20 ° C., and rapidly cooled. To obtain an unstretched film having a thickness of 99 ⁇ m. The Tg of the unstretched film was 50 ° C. The unstretched film is guided to a tenter, and with both ends of the film gripped by clips, it is preheated until the film temperature reaches 90 ° C.
  • Example 2 Polyester A, polyester B, and polyester C were mixed at a mass ratio of 7: 3: 90 and charged into an extruder to obtain an unstretched film having a thickness of 99 ⁇ m as in Example 1.
  • the Tg of the unstretched film was 48 ° C.
  • the unstretched film is guided to a tenter, and with both ends of the film gripped by clips, it is preheated until the film temperature reaches 88 ° C. (Tg + 40 ° C.), and then laterally at a film temperature of 53 ° C. (Tg + 5 ° C.). It was stretched 5 times. At this time, the distance between the clips in the longitudinal direction was shortened, and 1% relaxation (relaxation) was performed in the longitudinal direction.
  • the film stretched in the width direction was heat-fixed at 55 ° C (Tg + 7 ° C).
  • Tg + 7 ° C 55 ° C
  • a uniaxially stretched film of about 20 ⁇ m was continuously formed over a predetermined length to obtain a film roll made of a heat-shrinkable polyester film. ..
  • the film forming conditions are shown in Table 2, and the evaluation results are shown in Table 3. It was a film that had no problem in practical use in terms of shrinkage finish and bag drop evaluation.
  • Example 3 Polyester A, polyester B, and polyester C were mixed at a mass ratio of 57: 3: 40 and charged into an extruder to obtain an unstretched film having a thickness of 99 ⁇ m as in Example 1.
  • the Tg of the unstretched film was 63 ° C.
  • the unstretched film is guided to a tenter, and with both ends of the film gripped by clips, it is preheated until the film temperature reaches 103 ° C (Tg + 40 ° C), and then laterally at a film temperature of 68 ° C (Tg + 5 ° C). It was stretched 5 times. At this time, the distance between the clips in the longitudinal direction was shortened, and 1% relaxation (relaxation) was performed in the longitudinal direction.
  • the film stretched in the width direction was heat-fixed at 70 ° C. (Tg + 7 ° C.). By cutting and removing both edges of the stretched film, a uniaxially stretched film of about 20 ⁇ m was continuously formed over a predetermined length to obtain a film roll made of a heat-shrinkable polyester film. .. Then, the characteristics of the obtained film were evaluated by the above method.
  • the film forming conditions are shown in Table 2, and the evaluation results are shown in Table 3. It was a film that had no problem in practical use in terms of shrinkage finish and bag drop evaluation.
  • Example 4 Polyester A, polyester B, and polyester C were mixed at a mass ratio of 77: 3: 20 and charged into an extruder to obtain an unstretched film having a thickness of 79 ⁇ m as in Example 1.
  • the Tg of the unstretched film was 70 ° C.
  • the unstretched film is guided to a tenter, and with both ends of the film gripped by clips, it is preheated until the film temperature reaches 115 ° C (Tg + 45 ° C), and then laterally at a film temperature of 75 ° C (Tg + 5 ° C). It was stretched four times. At this time, the distance between the clips in the longitudinal direction was shortened, and relaxation was performed by 2% in the longitudinal direction.
  • the film stretched in the width direction was heat-fixed at 77 ° C. (Tg + 7 ° C.). By cutting and removing both edges of the stretched film, a uniaxially stretched film of about 20 ⁇ m was continuously formed over a predetermined length to obtain a film roll made of a heat-shrinkable polyester film. .. Then, the characteristics of the obtained film were evaluated by the above method.
  • the film forming conditions are shown in Table 2, and the evaluation results are shown in Table 3. It was a film that had no problem in practical use in terms of shrinkage finish and bag drop evaluation.
  • Example 5 Polyester A, polyester B, and polyester C were mixed at a mass ratio of 57: 3: 40 and charged into an extruder to obtain an unstretched film having a thickness of 118 ⁇ m as in Example 1.
  • the Tg of the unstretched film was 63 ° C.
  • the unstretched film is guided to a tenter, and with both ends of the film gripped by clips, it is preheated until the film temperature reaches 103 ° C (Tg + 40 ° C), and then laterally at a film temperature of 68 ° C (Tg + 5 ° C). It was stretched 6 times. At this time, the distance between the clips in the longitudinal direction was shortened, and relaxation was performed by 2% in the longitudinal direction.
  • the film stretched in the width direction was heat-fixed at 70 ° C. (Tg + 7 ° C.). By cutting and removing both edges of the stretched film, a uniaxially stretched film of about 20 ⁇ m was continuously formed over a predetermined length to obtain a film roll made of a heat-shrinkable polyester film. .. Then, the characteristics of the obtained film were evaluated by the above method.
  • the film forming conditions are shown in Table 2, and the evaluation results are shown in Table 3. It was a film that had no problem in practical use in terms of shrinkage finish and bag drop evaluation.
  • Example 6 Polyester A, polyester B, and polyester C were mixed at a mass ratio of 57: 3: 40 and charged into an extruder to obtain an unstretched film having a thickness of 79 ⁇ m as in Example 1.
  • the Tg of the unstretched film was 63 ° C.
  • the unstretched film is guided to a tenter, and with both ends of the film gripped by clips, it is preheated until the film temperature reaches 103 ° C (Tg + 40 ° C), and then laterally at a film temperature of 68 ° C (Tg + 5 ° C). It was stretched four times. At this time, the distance between the clips in the longitudinal direction was shortened, and 1% relaxation (relaxation) was performed in the longitudinal direction.
  • the film stretched in the width direction was heat-fixed at 70 ° C. (Tg + 7 ° C.). By cutting and removing both edges of the stretched film, a uniaxially stretched film of about 20 ⁇ m was continuously formed over a predetermined length to obtain a film roll made of a heat-shrinkable polyester film. .. Then, the characteristics of the obtained film were evaluated by the above method.
  • the film forming conditions are shown in Table 2, and the evaluation results are shown in Table 3. It was a film that had no problem in practical use in terms of shrinkage finish and bag drop evaluation.
  • Example 7 A film roll having a thickness of 15 ⁇ m was obtained by the same method as in Example 1 except that the thickness was changed to 74 ⁇ m by lowering the discharge of the extruder and winding the molten resin around a rotating metal roll and quenching the resin. Then, the characteristics of the obtained film were evaluated by the above method.
  • the film forming conditions are shown in Table 2, and the evaluation results are shown in Table 3. It was a film that had no problem in practical use in terms of shrinkage finish and bag drop evaluation.
  • Example 8 A film roll having a thickness of 40 ⁇ m was obtained by the same method as in Example 1 except that the thickness was changed to 198 ⁇ m by lowering the discharge of the extruder and winding the molten resin around a rotating metal roll and quenching. Then, the characteristics of the obtained film were evaluated by the above method.
  • the film forming conditions are shown in Table 2, and the evaluation results are shown in Table 3. It was a film that had no problem in practical use in terms of shrinkage finish and bag drop evaluation.
  • Polyester A, polyester B, and polyester C were mixed at a mass ratio of 77: 3: 20 and charged into an extruder to obtain an unstretched film having a thickness of 80 ⁇ m as in Example 1.
  • the Tg of the unstretched film was 70 ° C.
  • the unstretched film is guided to a tenter, and with both ends of the film gripped by clips, it is preheated until the film temperature reaches 75 ° C (Tg + 5 ° C), and then laterally at a film temperature of 75 ° C (Tg + 5 ° C). It was stretched four times.
  • the film stretched in the width direction was heat-fixed at 77 ° C. (Tg + 7 ° C.).
  • a uniaxially stretched film of about 20 ⁇ m was continuously formed over a predetermined length to obtain a film roll made of a heat-shrinkable polyester film. .. Then, the characteristics of the obtained film were evaluated by the above method.
  • the film forming conditions are shown in Table 2, and the evaluation results are shown in Table 3.
  • the piercing strength was low, the refractive index in the longitudinal direction was high, and there were defects such as bag breakage and holes in the bag drop evaluation.
  • Polyester A, polyester B, and polyester D were mixed at a mass ratio of 17: 3: 80 and charged into an extruder to obtain an unstretched film having a thickness of 80 ⁇ m as in Example 1, but the Tg was increased. Since the temperature was as low as 38 ° C., it adhered to the cooling roll, and an unstretched film could not be continuously obtained, so that film formation could not be evaluated.
  • Polyester A, polyester B, and polyester C were mixed at a mass ratio of 92: 3: 5 and charged into an extruder to obtain an unstretched film having a thickness of 99 ⁇ m as in Example 1.
  • the Tg of the unstretched film was 75 ° C.
  • the unstretched film is guided to a tenter, and with both ends of the film gripped by clips, it is preheated until the film temperature reaches 115 ° C (Tg + 40 ° C), and then laterally at a film temperature of 80 ° C (Tg + 5 ° C). It was stretched 5 times. At this time, the distance between the clips in the longitudinal direction was shortened, and 1% relaxation (relaxation) was performed in the longitudinal direction.
  • the film stretched in the width direction was heat-fixed at 82 ° C (Tg + 7 ° C).
  • Tg + 7 ° C By cutting and removing both edges of the stretched film, a uniaxially stretched film of about 20 ⁇ m was continuously formed over a predetermined length to obtain a film roll made of a heat-shrinkable polyester film. ..
  • the film forming conditions are shown in Table 2, and the evaluation results are shown in Table 3.
  • the shrinkage rate of hot water in the width direction measured at 90 ° C. for 10 seconds was low, the shrinkage was insufficient in the shrinkage finish evaluation, and the shrinkage finish and bag drop evaluation could not be performed.
  • Polyester A, polyester B, and polyester C were mixed at a mass ratio of 17: 3: 80 and charged into an extruder to obtain an unstretched film having a thickness of 101 ⁇ m as in Example 1.
  • the Tg of the unstretched film was 50 ° C.
  • the unstretched film is guided to a tenter, and with both ends of the film gripped by clips, it is preheated until the film temperature reaches 90 ° C. (Tg + 40 ° C.), and then laterally at a film temperature of 55 ° C. (Tg + 5 ° C.). It was stretched 5 times. At this time, the distance between the clips in the longitudinal direction was widened, and 2% stretching was performed in the longitudinal direction.
  • the film after being stretched 5 times in the width direction and 1.02 times in the longitudinal direction was heat-fixed at 57 ° C. (Tg + 7 ° C.).
  • Tg + 7 ° C. 57 ° C.
  • a uniaxially stretched film of about 20 ⁇ m was continuously formed over a predetermined length to obtain a film roll made of a heat-shrinkable polyester film. ..
  • the film forming conditions are shown in Table 2, and the evaluation results are shown in Table 3.
  • the refractive index in the longitudinal direction was high, and there was a defect that bag breakage occurred in the bag drop evaluation.
  • the heat-shrinkable polyester film of the present invention has a high heat-shrinkability, it has an excellent bag-dropping property, so that it can be suitably used for labeling applications such as containers.
  • the package such as a container obtained by using the heat-shrinkable polyester film of the present invention as a label has a beautiful appearance and is excellent in durability such as a bag.

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Abstract

L'invention a pour objet de fournir un film à base de polyester thermorétractable qui présente un retrait thermique élevé dans sa direction principale de retrait, qui présente également une solidité élevée à la perforation de film et une résistance à la rupture lors de la chute d'une bouteille, et qui est doté d'une excellente sensation de rigidité du fait de la densité élevée du film.　Plus précisément, l'invention concerne un film à base de polyester thermorétractable qui comprend 60% en moles ou plus à 95% en moles ou moins d'une unité éthylène téréphtalate pour 100% en moles de l'ensemble des unités ester, et 5% en moles ou plus à 40% en moles ou moins d'un diéthylène-glycol pour 100% en moles des composants polyalcool, et qui simultanément comprend 0% en moles ou plus à 5% en moles ou moins d'une unité constitutive dérivée d'un composant monomère susceptible de constituer un composant non cristallin pour l'ensemble des composants de résine polyester. Le retrait thermique en eau chaude lorsque le film est immergé pendant 10 secondes dans une eau chauffée à 90°C, la solidité à la perforation du film, la densité du film et l'indice de réfraction dans la direction longitudinale du film, se situent à l'intérieur de plages prédéfinies.
PCT/JP2021/027385 2020-07-29 2021-07-21 Film à base de polyester thermorétractable, étiquette thermorétractable, et corps d'emballage WO2022024936A1 (fr)

Priority Applications (5)

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US18/006,521 US20230348661A1 (en) 2020-07-29 2021-07-21 Heat-shrinkable polyester-based film, heat-shrinkable label, and packaging body
JP2022540254A JP7364085B2 (ja) 2020-07-29 2021-07-21 熱収縮性ポリエステル系フィルム、熱収縮性ラベル、及び包装体
EP21849664.4A EP4190845A4 (fr) 2020-07-29 2021-07-21 Film à base de polyester thermorétractable, étiquette thermorétractable, et corps d'emballage
KR1020237006647A KR20230042741A (ko) 2020-07-29 2021-07-21 열수축성 폴리에스테르계 필름, 열수축성 라벨 및 포장체
CN202180059666.2A CN116133825A (zh) 2020-07-29 2021-07-21 热收缩性聚酯系薄膜、热收缩性标签、及包装体

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See also references of EP4190845A4

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US20230348661A1 (en) 2023-11-02
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